Disazo compounds



United States Patent 2,795,571 DISAZO COMPOUNDS James F. Feeman, West Reading, Pa., assignor to Althouse Chemical Co., Worcester, Mass., a corporation of Massachusetts No Drawing. Application July 6, 1956, Serial No. 596,149

11 Claims. (Cl. 260-153) (Structure 1) wherein X is a whole number less than 4; R1 is a radical selected from the group consisting of (wherein n is a radical selected from the group consisting of -H, lower alkyl, O- lower alkyl, halogen, COOH, OCH2COOH and SO3H; y is a whole number less than 3; and Z is a radical selected from the group consisting of -CH:CH--, NHCO-, and NHCONH); R2 is a radical selected from the group consisting of -H, -lower alkyl, OCH2COOH, -O- lower alkyl, -NH- acyl, lower alkyl-OH, and --O lower alkyl OH; 1 is a whole number less than 3; and Y is a radical selected from the group consisting of --CO-, CO-CH=CRs-CO (wherein R2 is a radical selected from the group consisting of -H, Br, -Cl, and -CH3),

and

HNIu

(wherein R4 is a radical selected from the group consisting of -H, -lower alkyl, -phenyl, and lower alkylated phenyl),

l Ce s Hereinafter the above will sometimes be referred to as Structure I.

The dotted linkages, whenever shown indicate bonding of substituent groups to ring nuclei at any available positions in the entire ring structure providing stable linkages.

The triazole structure of the naphthotriazole moiety is sometimes illustrated in the following ways:

and

According to another aspect of the invention, it has been found that the amino-azo compounds referred to just below are useful as dye intermediates for the production of Structure I type compounds as well as other disazo dyes. These amino-azo compounds have the following structure (sometimes hereinafter referred to as N (in) (Ho s):-

(Struetura 11) wherein R1, R2, x and z represent the same substituents as in Structure I. Such amino-azo compounds can be effectively condensed with suitable reagents as more fully described hereinafter to produce various disazo dyes.

Structure 1 type compounds can be prepared by coupling a diazotized aminonitroaryl compound with a naphthylaminesulfonic acid. The amino-azo compound is then oxidized to form a nitroarylnaphthotriazole which compound is then reduced to form an aminoarylnaphthiotriazole. The aminoarylnaphthotriazole so produced is diazotized. The diazotized aminoarylnaphthotriazole is then coupled in para position to an amine of the benzene series. This forms the aniino-azo intermediate (Structure H) which is thereafter condensed with a suitable reagent as more fully hereinafter described to form the disazo dye.

The Structure II type compounds can also be produced by using acylamino-aminoaryl compounds in place of the nitro-aminoaryl compounds in the coupling reaction with the naphthylaminesulfonic acid. When proceeding in this manner, following the formation of the amino-azo compound and subsequent triazolation by means of a suitable oxidizing agent, the acylamino-arylnaphthotriazolesulfonic acid is saponified to the desired amino compound by the use of an alkaline or acidic hydrolytic agent.

Certain compounds according to Structure II above may also be prepared by an alternative method which is as follows: one mol of a diaminoaryl compound, e. g., benzidine, o-tolidine 4,4 diamino 3 biphenylsulfonic acid, etc., which has been tetrazotized, and which gives a water soluble tetrazonium salt, is coupled by means of one of its diazonium groups to one mol of a suitable naphthylaminesulfonic acid. Upon completion of this coupling reaction, the second diazonium group of the tetrazonium salt is reacted with an amine of the benzene series which couples in para position (the order to these two couplings may be reversed in certain cases Where desired), to produce a diamino-disazo dye. The latter is then oxidized by means of a suitable reagent, well known to those versed in the art of dyestuff manufacture, e. g., a cupric salt, to the corresponding Structure II compound.

In the various compounds of the present invention the sulfonic acid radicals can be substituted at ditferent positions of the naphthotriazole nucleus than those shown in the illustrative examples. The number and positioning of the sulfonic acid radicals will depend on the structure of the naphthylaminesulfonic acid which is initially coupled with the diazotized aminonitroaryl or diaminoaryl compound. Useful naphthylaminesulfonic acids which permit coupling in ortho position to the amino group are for example: naphthionic acid, 6'amino-l-naphthalenesulfonic acid, 6-amino-Z-naphthalenesulfonic acid, 7- amino l naphthalenesulfonic acid, 4-amino-2-naphthalenesulfonic acid, 3-amino-l, S-naphthalenedisulfonic acid, 3-amino-2,7-naphthalenedisulfonic acid, 4-amino- 1,fi-naphthalenedisulfonic acid, S-amino-Z,7-naphthalenedisulfonic acid, 6-amino-l,3-naphthalenedisulfonic acid, 7 amino 1,3 naphthalenedisulfonic acid, 8-amino-1,6- naphthalenedisulfonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 7 amino 2,4,G-naphthalenetrisulfonic acid, 8-amino-l,3,S-naphthalenetrisulfonic acid, S-aminol,3,6-naphthalenetrisulfonic acid, etc.

Useful dyes having good light-fast and wash-fast characteristics can be prepared from the mono, di and tri sulfonic acids of the naphthylamines. However, When the dyes are to be applied to fibrous materials containing a mixture of synthetics such as nylon or acetate and cellulosic fibers, it is preferred to have a total of 3 sulfonic acid radicals in the Structure II intermediate when R1 is to have a total of 3 or 4 sulfonic acid radicals in the Structure II intermediate when R1 is and to have a total of 4 sulfonic acid radicals in the Structure II intermediate when R1 is The reasons for this are that the dyes of this invention having fewer sulfonic acid groups tend to stain nylon and acetate, while a higher number of sulfonic acid groups tends to decrease the afiinity of these dyes for the fiber.

In accordance with this invention, aminonitroaryl compounds which are useful are for example: p-nitroaniline, Z-amino-S-nitrobenzenesulfonic acid, Z-chloro- 4 4-nitroaniliue, 4-nitro-o-anisdine, 4-nitro-o-toluidine, 4'- nitro-4-biphenylamine, 4-amino-4-nitrostilbene, 4-arnino- 4-nitro-2,2'-stilbene-disulfonic acid, 4'-amino-4-nitrobenzanilide, 4-amino-4'-nitrocarbanilide, 4,4-diamino- 3,3 biphenyldicarboxylic acid, 4,4 diamino 3,3-biphenyldiglycollic acid, etc.

Acylamino-aminoaryl compounds which correspond to the nitroaminoaryl compounds above, as for example, 4- aminoacetanilide, 2 amino-5-acetaminobenzenesulfonic acid, 4' acetamino 4 biphenylamine, 4'-acetamino-4- amino-2,2'-stilbenedisulfonic acid, etc., can also be coupled in a similar manner with naphthylamine-sulfonic acids in the production of dyes and dye intermediates of the type herein contemplated.

Oxidation of the nitro-amino-azo compounds to form the nitroarylnaphthotriazoles can be effected by means of reagents and techniques well known to those skilled in the art, as for example, by means of cupric ammonium hydroxide solution,

The reduction of the nitroarylnaphthotriazoles to form the aminoarylnaphthotriazoles can be efiected in the usual manner, as for example by means of powdered iron in dilute acetic acid solution.

Diazotization of the amino-arylnaphthotriazole can be effected in any suitable manner, either directly or indirectly. Such diazotization reactions are well known to those skilled in the art.

Suitable arylamines for coupling with the diazotized aminoarylnaphthotriazoles are preferably those which can be coupled according to conventional techniques in para position to the amino group, and include such compounds as aniline, o-toluidine, m-toluidine, o-anisidine, m-anisidine, o-phenetidine, m-phenetidine, S-methylo-anisidine, 3 amino acetanilide, 2,3 xylidine, 2,5- xylidine, 2,6-Xylidine, 3,5-xylidine, 2,5-dimethoxyaniline, 2,5-diethoxyaniline, 3'-aminoformanilide, 3'-amino-4'- methoxyacetanilide, o-amino-mandelic acid, m-aminophenethylalcohol, 2-(3-amino) phenoxyethanol, etc.

In a preferred embodiment of this invention, two mols of an intermediate having Structure II are condensed with one mol of a condensing agent such as phosgene, a dicarboxylic acid dihalide, a cyanuric halide or a suitable heterocyclic dihalide which will yield radicals of the type given for Y in Structure 1.

Such condensations can also be effected by terephthaloyl chloride, l,4-dichlorophthalazine, 2,4-dichloro- 6 phenyl s triazine, 2,6-dichloro-S-methyl-pyrimidine, 2,4-dichloro-quinazoline.

To minimize cost of reactants in preparing compounds according to the invention, it is preferred to condense the wherein R3 and R4 represent substituent groups according to Structure I above.

Still further in order to minimize material costs and also to simplify the production technique, it is preferred that the R1 radicals of Structure I be selected from the following group:

QCH=CHQ SOIH Boss and Particularly good dye characteristics such as light-fastness and wash-fastness are obtained where the Y linkage and the R1 radicals are selected from the groups referred to just above and where, in addition, the R2 radicals of Structure I above are selected from the following groups:

and

NHCOCHs When fumaroyl chloride and cyanuric chloride are used to condense the amino-azo intermediates which form yellow dyes, the dyes so produced tend to be somewhat greener than when the same azo intermediates are condensed with phosgene. Cyanuric chloride is highly desirable as a condensing reagent for the azo compounds because it permits the formation of unsymmetrical dye molecules and in this way it is possible to vary the shade of the color and the dyeing properties of the dyestuflf.

When cyanuric chloride is used as the condensing reagent the third chlorine can be replaced by reacting the condensation product with aniline as described in Example 5, or by the use of other reagents such as ammonia, lower alkyl amines or lower alkylated anilines.

Equivalent amounts of other condensing agents, such as fumaroyl bromide or dichlorides or dibromides of maleic, mesaconic, citraconic, bromofumaric, chlorofumaric, chloromaleic or bromomaleic acids, can be used in lieu of fumaroyl chloride to effect condensations of the type generally illustrated by Example 18.

These new disazo compounds are water soluble and are particularly useful as substantive dyes to impart yellow and orange shades to cellulosic fibers. A wide variety of color shades are obtainable by employing various of the compounds contemplated. When use-d as dyestuffs, they have been found to possess excellent atfinity for cellulose; they show outstanding dyeing properties; the colors are fast to light and the dyeings have good wash-fastness. The wash-fastness and light-fastness of the colors are not adversely affected by conventional after-treatments with heat hardenable resins used in various fabric finishing processes to impart desirable properties or effects to the fabric (e. g., stabilization, crease-proofing, durabilizing mechanical finish effects, etc.), and conventional dye fastening agents (usually cationic resinous materials or amino-aldehyde condensation products) used to increase wash-fastness of the dyeings have a far less adverse effect on the light-fastness of the dyes of this invention than on comparable yellow and orange dyes heretofore available.

A rather striking characteristic of these new disazo dyes is their high light-fastness even though the dye molecule is not metallized (i. e., does not contain copper). Therefore, these dyes can be used in many instances where the combination of wash and light-fastnesses are desirable but where metallized dyes are unsuitable, e. g, in the dyeing of rubber-backed fabrics.

Compounds according to the invention can be prepared as set forth in the following illustrative examples. In these examples, unless otherwise indicated, parts are by weight, temperature is given in degrees centigrade and percentages are percentages by weight.

Niki-ONE:

HOIS

H055 SOsH (Compound In) (sometimes hereinafter referred to as Compound In which can be prepared by coupling diazotized p-nitroaniline with S-amino-l,3,o-naphthalenetrisulfonic acid, oxidizing the amino-azo dye thus produced to the corresponding 2- (4'-nitrophenyl) naphtho-( 1,2)triazole 4,7,9 trisulfonic acid, and reducing the nitro group to an amino group) is diazotized directly in aqueous solution at 0 and coupled with 10.7 parts of m-toluidine at pH 3.0-4.0. This aminoazo dye (sometimes hereinafter referred to as Compound Ib) is then reacted with phosgene at 2540 and pH 6.5-7.5 in aqueous solution until free amino group is no longer detectable. The resultant new dye is then filtered and dried. It has the formula Hots N N-ON=N NH- l H HOsS SOtH HOsS N -1T- =N NH- N Nnooorn -oo notssum 2 and is a brown-yellow powder which dyes cotton and re generated cellulose directly from aqueous solution in yellow-orange shades of very good fastness to light and to washing.

Example 3 In Example 1, while otherwise proceeding as described, if the 10.7 parts of m-toluidine are replaced with 13.7 parts of S-methyl-o-anisidine, a new dye is produced which has the formula OCH! SO H

It is a red-brown powder which dyes cotton and regenerated cellulose in orange shades of excellent fastness to washing and very good fastness to light.

Example 4 61.8 parts of the amino-azo compound (Compound lb), prepared as described in Example 1, are dissolved in neutral aqueous solution, by means of 900 parts of water, at 40. While stirring, vigorously, a solution of 9.2 parts of cyanuric chloride in 50 parts of acetone, and another solution containing sodium carbonate in water, are added dropwise slowly to the dye solution, the sodium carbonate being added in suflicient amount to keep the by dissolving it in 1500 parts of water with the addition reaction at pH 6.5 to 7.5. After the cyanuric chloride f di m hydroxide to raise the pH to 11, heating to solution has been added, the temperature is maintained adding 30 parts of activated charcoal and 50 parts at 40 for thlrty than reused to 90 and of a siliceous filtering aid, filtering, and salting the aminoarts of aniline added, and the tem erature maintained s for an additional hour The 5 dye is separated azo compound from solution by addition of sodium chloby addition of Sodium chloride, filtered, and dried It ride. After filtering the intermediate, it is reacted in is a yellow-brown powder which dyes cotton and regenaqueous solution at P f at 10 with erated cellulose in yellow shades of excellent fastness to Phosgene until free ammo group longer P light and washing, and it has the formula: 10 The resultant new dye is precipitated from solution by H015 SOQH HB ICuHs Example 5 addition of sodium chloride, filtered and dried. It has A solution is prepared from 18.4 parts of benzidine, the formula parts of 30% hydrochloric acid and 200 parts of water and is a yellow-brown powder which dyes cotton and re at 90. The solution is allowed to cool to 60; 20 parts 30 generated cellulose in clear yellow shades of excellent of 30% hydrochloric acid are added; and the resultant fastness to light and to washing.

suspension of benzidine dihydrochloride is cooled to 10 by the addition of ice. Then 14 parts of sodium nitrite, Example 6 as a 30% solution in water, are added during five minutes, the temperature being maintained at 10 by further Parts of the compound of the formula addition of ice as needed. After completion of the diazotization, the excess of nitrous acid is removed by N N on=crr addition of sulfamic acid, in amount sufiicient to produce a negative test when the clear tetrazonium salt solution 110 s N 0,11 H033 is spotted on starch-iodide paper.

Ice is then added to the solution to lower the temperature to 0, and 30 parts of sodium bicarbonate are sifted into the solution. 25 parts of pyridine are added, fol- S0311 (Compound VIa) lowed immediately by a solution prepared from 42 parts of S-amino-l,3,S-naphthalenetrisulfonic acid, 100 parts 45 (hereinafter sometimes referred to as Compound VIa, of water and sufficient sodium carbonate to raise the pH prepared by coupling diazotized 4-amino-4'-nitro-2,2'-

of the solution to 7.5. Coupling is allowed to proceed stilbenedisulfonic acid with 6-amino-1,3-naphthalenediat 0-5 for 16 hours. The pH of the mixture is then sulfonic acid, oxidizing the nitroamino-azo compound lowered to 5.5 with 25 parts of glacial acetic acid, and a thus produced with cupric ammonium hydroxide solution solution of 12 parts of m-toluidine in 25 parts of water to the corresponding nitro-naphtho (1,2)triazone, and and 12 parts of 30% hydrochloric acid is added. The reducing the nitro group with iron powder in dilute acetic temperature of the coupling is allowed to rise to 20 acid solution) are diazotized directly in aqueous solution, during three hours. The coupling mixture is then treated and coupled at pH 3.5-4.5 with 10.7 parts of m-toluidine. with 28 parts of sodium hydroxide and the temperature is The amino-azo compound thus produced is then reacted raised to and held at this temperature during the with phosgene in aqueous solution at pH 6.5-7.5 and addition of 50 parts of crystalline copper sulfate penta- 25 to 50 until free amino group is no longer present. hydrate, and for one hour additional. parts of 30% The new dye which precipitates is filtered and dried. It hydrochloric acid are then added, and the precipitated is an orange-brown powder which dyes cotton and rehydrochloride of the intermediate of the formula generated cellulose in yellow shades of excellent fastness N CHI (Compound Vb) (hereinafter sometimes referred to as Compound Vb) to light and to washing. It has high tinctorial strength is filtered. This amino-azo compound is further purified and has the formula H 0:8 N 0111 H O: O

Example 7 68.3 parts of the Compound Vla are diazotized directly and coupled at pH 4.5 to 5.5 with 18.7 parts of anilinomethanesulfonic acid in aqueous solution at completion of the coupling reaction, enough sodium hydroxide is added to produce a 4% NaOH solution. The temperature of the reaction is maintained at 90 for one Upon 5 ous solution at 0, and coupled at pH 3.0-4.0 with 10.7 parts of m-toluidine. The amino-azo dye thus produced is then reacted with phosgene at -60 and pH 6.5-7.5 until free amino group is no longer detectable. The resultant new dye which precipitates is then filtered and dried. It is a yellow-brown powder which dyes cotton and regenerated cellulose in yellow shades of excellent fastness to light and washing. It has the formula hour, at the end of which time the amino-azo dye of the formula Hots- SOaH is isolated by neutralization of the reaction with concentrated hydrochloric acid and addition of sodium chloride.

The amino-azo dye, further purified, if desired, by reprecipitation from acid solution and then from alkaline aqueous solution with sodium chloride, is reacted in aqueous solution at pH 6.5-7.5 and 25-40 with phosgcnc, until free amino group is no longer detectable. resultant new dye is then filtered and dried. It has the formula HOzS- HOsS and is a yellow-brown powder which dyes cotton and regenerated cellulose in yellow shades of excellent fastness to light and to washing.

Example 8 60.3 parts of the compound of the formula 05 80311 (prepared in the same manner as Compound VIa but using naphthionic acid instead of the 6-amino-l,3-naphthalenedisulfonic acid) are diazotized indirectly in aque- The Example 9 68.3 parts of the Compound VIa are diazotized directly neutral. After all the fumaroyl chloride has been added, stirring is continued until no more free amino group can be detected. Then the new dye is separated from solution with the aid of sodium chloride, and the precipitated dye is filtered and dried. it is an orange-brown powder which has the formula and which dyes cotton and regenerated cellulose in yellow shades of excellent light and washing fastness.

Example 10 68.3 parts of Compound Vla are diazotized and coupled with 10.7 parts of m-toluidine as described in Example 6. The amino-azo compound thus produced is dissolved in neutral aqueous solution at While stirring vigorously, a solution of 9.2 parts of cyanuric chloride in parts of acetone, and another solution of sodium carbonate, are added slowly, dropwise, to the dye solution, the sodium carbonate solution being added in sufli- Example 13 cient amount to keep the reaction at pH 6.5-7.5. After the cyanuric chloride solution has been added completely, if 55 21 :gi xg iigg z gfiig ggg f g f g ig gfii the temperature is maintained at for 30 minutes, and pound of the formula p the pH is maintained at 6.57.5. Then the temperature 5 is raised to and 4.7 parts of aniline are added. The H033 03:01; temperature is maintained at 90 for an additional hour. The new dye, thus produced, is separated from solution N 0311 H0 by salting, filtered and dried. It is an orange-brown powder which dyes cotton and regenerated cellulose in 10 yellow shades of excellent fastness to light and washing.

It has the formula (prepared in the same manner as Compound VIa but Hois \-N 60111 H038 i311:

Example 11 using 7-amino-1,3-naphthalenedisulfonic acid instead of 6-amino-1,3-naphthalenedisulfonic acid) a new dye is In Example 6, while otherwise proceeding as described, 0d d h h if the 10.7 parts of m-toluidine are replaced with 13.7 fi fi t :5 1 at propemes to that of Example H038 Nil? CH=OHQ N=N-QNH- N OsH Hos H: "C! O parts of S-methyl-o-anisidine, a new compound is pro- Example 14 duced which has the formula In Example 6, while otherwise proceeding as described,

OCH:

HOrS \N 01H HOa S H1 =00 if the Compound VIa is replaced with 68.3 parts of the It is a red-brown powder which dyes cotton and regenercompound of the formula ated cellulose in orange shades of excellent fastness to NN- CH=CH NH: light and to washing. Q Q

N 03H H03 Example 12 HOaS- SOIH In Example 6, while otherwise proceeding as dep und XIVa scribed, 11 the 10.7 parts of rn-toluidine are replaced with (sometimes hereinafter referred to as Compound XIVa,

prepared in the same manner as Compound VIa but using 15.0 arts of 3'-aminoacetanilide, a new d 'e is roduced p 3 p 55 3-am1no-2,7-naphthalenedrsulfomc acid instead of 6- which dyes cotton and regenerated cellulose in orangeaminoq,3 naphthalenedisulfonic acid) a new dye is yellow shades of very good fastness to light and to washduced which has the formula \N 01H H03 H: =00

HOsS 0a 2 ing. It is an orange-brown powder which has the forand which has similar properties to the dye produced in mula Example 6.

r|-r r' 0H=c H- N==N NH- HOsS N 0111 B01 NHOOCH: Co

13 Example reprecipitation at by means of hydrochloric acid to pH 1.5 and filtration. The intermediate thus produced In Example 9, while other-vise proceeding as described, is then diazotized indirectly by solution at pH 7 in 500 if the 68.3 parts of Compound VIa are replaced with parts of water. addition to the solution of 4 parts of 68.3 parts of Compound XlVa, a new dye is produced 5 sodium nitrite, and addition of the solution thus obtained which has the formula to 20 parts of 30% hydrochloric acid and ice sufiicient to N OgH H0: 3

HO S SOBH 2 and which has similar properties to the dye produced in 15 keep the temperature at 0 for a period of two hours.

Example 9. Excess nitrous acid is removed by the adddition of Example 16 enough sulfamic acid to produce a negative test when the diazotization mixture is spotted on starch-iodide paper.

In Example 10, while otherwise proceeding as described, 6 parts of m-toluidine are then added and the pH is adif the 68.3 parts of Compound VIa are replaced with 68.3 20 justed to 3.0-3.5 with sodium acetate solution until couparts of Compound XlVa, a new dye is produced having pling is completed. The amino-azo compound thus prosimilar properties to those of the dye produced in Exduced is filtered at 20 and at pH 1.5; the filter cake is ample 10, but having the formula redissolved at pH 8 in 500 parts of water, purified by it 2 O Example 17 parts of Compound Ia are dissolved at pH 7 in 500 5 addition at 70 of 10 parts of activated charcoal and parts of water at 75. To this solution are added 1 part filtration. of a non-ionic surface-active dispersing agent, 25 parts of The solution of the amino-azo compound thus prosodium acetate and 25 parts of p-nitrobenzoyl chloride duced which has the formula Hots N NONHCOON=NQNEH HO:S 80311 is then reacted at pH 6.5-7.5 and 25 with phosgene with vigorous agitation. After ten minutes at 75, the until free amino group is no longer detectable. The retemperature is raised to 95 and 50 parts of iron powder sultant new dye is filtered and dried. It is an orange are added during 15 minutes. The temperature is then 50 powder which dyes cotton and regenerated cellulose in held at 95-l00 for 30 minutes, the reaction is made yellow shades having excellent fastness to light and to alkaline by the addition of sodium carbonate until the washing. It has the formula Hots N N- 'NHCO N=N@NH A OHl =00 H038 SOIH 2 pH is 9.0, and the solution of the compound of the Example 18 fomma 69.5 parts of the amino-azo Compound Vb used to prepare the dye in Example 5 are reacted with 7.65 parts H033 T of fumaroyl chloride. While vigorously stirring the dye I intermediate solution, a solution of 7.65 parts of fumaroyl N chloride in 40 parts of benzene, and a sodium carbonate solution are added dropwise to the dye solution at 25-30, H0=s s0=H the sodium carbonate solution being added in sufiicient amount to keep the reaction constantly approximately is filtered to free it of precipitated inorganic material. To neutral. After all the fumaroyl chloride has been added, the clear pale-yellow solution is added 10% of sodium stirring is continued until no more free amino group is chloride. Cooling the solution with stirring produces a present. Then the new dye is separated from solution by precipitate which is filtered. The latter precipitate is resalting with sodium chloride and the precipitated dye dissolved in 500 parts of Water and further purified by is filtered and dried. The new dye produced is a yellowbrown powder which dyes cotton and regenerated cellulose 1n yellow shades of excellent fastness to light and washing. It has the formula :1 being a radical selected from the group consisting of -H, lower alkyl, O-lower alkyl, Cl, COOH, -OCH2COOH and SOsH; y being a whole number SOsH Example 19 69.5 parts of the amino-azo Compound Vb used to prepare the dye of Example 5 are dissolved in neutral aqueous solution at 40'. While stirring vigorously, 9.2 parts of cyanuric chloride in 50 parts of acetone and another solution of sodium carbonate are added slowly dropwise to the dye intermediate solution, the sodium carbonate solution being added in suflicient amount to keep the reaction at pH 6.5-7.5. After the cyanuric chloride solution has been added completely, the temperature is maintained at 40 for 30 minutes and the pH maintained at 6.5-7.5. Then the temperature is raised to 90 and 4.7 parts of aniline are added. The temperature is maintained at 90 for an additional hour. The new dye, thus produced, is separated from solution by salting. filtered and dried. The new dye produced is a yellow-brown powder which dyes cotton and regenerated cellulose in yellow shades of excellent fastness to light and washing. It has the formula H018 SOaH Example 20 The disazo compound (0.5 part), obtained according to Example 6, is dissolved in a dyebath which contains 2000 parts of Water. Cotton (100 parts) is entered at 40-60; the bath is heated to 90-95 within 30 minutes; 20 parts of sodium chloride are added; and dyeing is performed for 30 minutes more at this temperature. The dyebath is then well-exhausted of color. The dyed fabric is rinsed cold and dried. The cotton is dyed a reddishyellow shade of excellent fastness to light and very good fastness to washing.

The dyed fabric, when after treated with urea-form aldehyde in the usual manner Well-known in the trade, shows markedly increased fastness to washing with no decrease in light fastness.

I claim:

1. A disazo compound having the following structure (n) u (n) I and 2 less than 3; and Z being a radical selected from the group consisting of CH=CH, NHCO, and

NI-ICONH-; R2 is a radical selected from the group consisting of H, -lower alkyl, OCHzCOOH, O-lower alkyl, NH-acyl, lower alkylOH, and O-lower alkyl- OH; z is a Whole number less than 3 and Y is a radical selected from the group consisting of CO,

and

R3 being a radical selected from the group consisting of H, --Cl, Br, and CH3 and R4 being a radical selected from the group consisting of H, lower alkyl, -phenyl, and lower alkyl phenyl.

2. A disazo compound having the following structure:

wherein: 4. A compound according to claim 2 wherein R1 is x is a whole number less than 4; O R1 is a radical selected from the group consisting of and x is 3.

5. A compound according to claim 2 wherein R1 is and and x is 2. gunman-Q 6. A compound according to claim 2 wherein Y is C0--. 02H H013 7. A compound according to claim 2 wherein Y is CO-CH=CR3-CO and R3 is a radical selected from the group consisting of H, Br, Cl, and CH3.

8. A compound according to claim 2 wherein Y is R5 is a radical selected from the group consisting of and R4 is a radical selected from the group consisting of H, lower alkyl, phenyl, and lower alkylated phenyl.

1 9. The compound and 80 H035 N TON=N NEP Nncocm and Y is a radical selected from the group consisting of 2 -O0. COCH=IGR:OO 10 The compound HOaB N TON=NONH Hos 80:11

11. The compound OIH 2 and N References Cited in the file of this patent ('3 UNITED STATES PATENTS mm. 820,052 Kirchhoff et a1. May 8, 1906 R3 being a radical selected from the group consisting of 2,004,250 schmflhelm et June 11, 1935 1 and and 2,270,478 Schnud Jan. 20, 1942 R4 being a radical selected from the group consisting of 2,335,852 n Oct, 2, 1945 H, lower alkyl, phenyl and lowcr alkylated phenyl. 2,457,262 Kmght' P 12, 1949 3. A compound according to claim 2 wherein R is 5 Grandlean M31 23, 1954 O FOREIGN PATENTS and x is 3. 183,453 Switzerland June 16, 1936 

1. A DISAZO COMPOUND HAVING THE FOLLOWING STRUCTURE 